Tertiary alcohols



TERTIARY ALCOHOLS Henri Normant, Paris, France, assignor to Societe des Usines Chimiques Rhone-Poulenc, Paris, France, a French body corporate No Drawing. Application January 27, 1956 Serial No. 561,928

Claims priority, application France February 3, 1955 2 Claims. (Cl. 260- 638 in which the symbols R and R each represent a hydrogen atom or an alkyl group containing from 1 to 4 carbon atoms or an aryl group, the symbol R represents a hydrogen atom or a methyl group, and the symbols R R and R each represent a hydrogen atom or an alkyl group containing from 1 to 5 carbon atoms, one at least of the symbols R R and R representing an alkyl group. These new compounds have agreeable bergamot-lavender odours each with its own particular shade. They are accordingly useful in perfumery and the invention includes within its scope a perfume composition containing at least one diethylenic alcohol of the general Formula I.

By the expression a perfumery base material as used herein is meant a material or a mixture of materials which serves as a vehicle for odiferous compounds in the art of perfumery or cosmetics. The material or mixture of materials may, as in the perfumery art, serve merely to render the odiferous compounds convenient to handle and permit them to exhibit their properties advantageously or it may, as in the cosmetic art, have desirable properties of its own and be used as a vehicle for odiferous substances in order to render it more attractive for personal use. A perfumery base material used in perfumery may for example be ethyl alcohol or a concentrated aqueous solution thereof such as a solution of 80% by weight concentration. It may contain such additives as gums, balsams and oleo-resins for retarding its rate of evaporation. Other perfumery base materials may take the form of cold creams, hand lotions, hand creams, vanishing creams, face powders, face rouges, lipsticks, shampoos, hair oils, hair creams etc., compounded according to the methods and formulae well understood in the art from such products as waxes such as beeswax, or spermaceti, oils such as castor oil, mineral oils or lanolin, soaps, glycerine, surface active agents, gums, talc, chalk, kaolin, Water repellants such as zinc stearate, pigments, dyes and gums such as gum tragacanth. As will be understood by those skilled in the art the perfumery base material may have compounded therein other odiferous substances of synthetic or animal or vegetable origin in addition to one or more of the new compounds provided by the invention for the purpose of producing composite odours.

The invention also includes within its scope a new process for the preparation of the alcohols of general Forests Patent O 2,838,576 Patented June 10,

mula I. This process consists in condensing a 'y-ethylenic ketone of the general formula:

C=C-OHzCHgCOCH; II R; R3

with an ethylenic organo-magnesium derivative of the general formula:

R5 R /C XMg( 3 a in which general formulae the symbols R R R R R and R are as hereinbefore defined and the symbol X represents a halogen atom (preferably bromine), and then decomposing the complex obtained with water. The ethylenic organo-magnesium derivative ispreferably employed in excess and the complex is preferably decomprsed with a cold aqueous solution of ammonium chlon e.

The invention fu rther includes within its scope a modification of the said new process which can be applied to the preparation, of certain .known-diethylenic alcohols, for example linalool, in which modifications each one of the symbols R R and R represents a hydrogen atom.

The ethylenic organo-magnesium derivatives of Formula III can conveniently be prepared by reacting magnesium with a solution, in tetrahydrofuran, of an ethylenic compound of the general formula:

III

The advantage of the aforesaid process over the previously known process is evident from its application to the preparation of dl-linalool described in the first part of the example which follows. The synthesis of dl-lina- 1001 was carried out by Ruzicka and Fornasir, Helv. Chim. Acta, 2, 184 (1919), by adding a molecule of acetylene to a molecule of 2-methyl-l1ept-2-en-6-one and transforming the acetylenic triple bond of the reaction product into an ethylenic double bond by cautious hydrogenation. The process according to the invention permits the synthesis of dl-linalool in a single operation with an excellent yield.

The following example illustrates the process of the invention.

Example Magnesium (24 g.) is introduced into dry tetrahydrofuran (200 cc.) containing a trace of iodine and then a solution of vinyl bromide (107 g.) in an equal weight of tetrahydrofuran is added to it, drop by drop, with stirring. The magnesium solution thus obtained is cooled in ice. A solution of 2-methyl-hept-2-en-6-one (101 g.) in an equal volume of anhydrous ether is then added with vigorous stirring. When the addition is complete, the mixture is stirred for a further hour and then allowed to stand for 12 hours. ammonium chloride is then added to decompose the magnesium complex formed. The mixture separates into two layers; the organic layer is decanted and dried over anhydrous potassium carbonate, freed from solvents by heating on a water bath, and then rectified by distillation under reduced pressure. dl-linalool (103 g.) of good purity, representing a yield of 83%, separates at 83 to 85 C. under a pressure of 12.5 mm. of mercury.

By following the same procedure, there are also obtained with comparable yields the following new compounds which exhibited an agreeable bergamot-lavender odour in various shades:

Commencing with l-bromopropene, 2:6-dimethyl-nona- A saturated aqueous solution of p 3 2:7 dien 6 01, B. P. =99-100 C.; 11 :0864; n =1.4652.

Commencing with l-bromo-hept-l-ene, 2:6-dimethyltrideca-2z7-dien-6-ol, B. P. =154-156 C.; d =O.842; n =1.4661.

Commencing with l-bromoisobutene, 2:6:8-trimethylnona-2z7-dien-6-ol; B. P. =106l07 C.; 11 :0866; n =1.4692.

Commencing with 2-bromopropene, 2:6:7-trimethylocza 2:7 dien 6 01, B. P. =98-99 C.; 11 :0366; n =1.4658.

I claim:

1. A process for the preparation of diethylenic alcohols which comprises reacting magnesium with a solution in tetrahydrofuran of an ethylenic compound of the general formula:

wherein X is a halogen atom and R R and R are each selected from the class consisting of hydrogen atoms and alkyl groups of from 1 to 5 carbon atoms, condensing the ethylenic organo-magnesium derivative thus obtained with a 'y-ethylenic ketone of the general formula:

References Cited in the file of this patent UNITED STATES PATENTS 2,589,275 Naves Mar. 18, 1952 FOREIGN PATENTS 544,388 Germany Feb. 19, 1932 OTHER REFERENCES Krestinsky: Berichte d. d. c. Ges., vol. B (1922), pps. 2762-3.

Beilstein, Band I (first supplement), p. 240 (1928).

Naves Etudes Bull. Soc. Chim. (France) p. 507, table (1951).

Lewis et al.: I. A. C. 8., vol. 74 (1952), pps. 12537. 

1. A PROCESS FOR THE PREPARATION OF DIETHYLENIC ALCOHOLS WHICH COMPRISES REACTING MAGNESIUM WITH A SOLUTION IN TETRAHYDROFURAN OF AN ETHYLENIC COMPOUND OF THE GENERAL FORMULA: 